FR3053277A1 - AERONAUTICAL GLAZING COMPRISING AN ACRYLIC POLYMER SHEET WITH IMPROVED MECHANICAL PROPERTIES - Google Patents
AERONAUTICAL GLAZING COMPRISING AN ACRYLIC POLYMER SHEET WITH IMPROVED MECHANICAL PROPERTIES Download PDFInfo
- Publication number
- FR3053277A1 FR3053277A1 FR1656060A FR1656060A FR3053277A1 FR 3053277 A1 FR3053277 A1 FR 3053277A1 FR 1656060 A FR1656060 A FR 1656060A FR 1656060 A FR1656060 A FR 1656060A FR 3053277 A1 FR3053277 A1 FR 3053277A1
- Authority
- FR
- France
- Prior art keywords
- sheet
- glazing
- modified acrylic
- pmma
- casting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000058 polyacrylate Polymers 0.000 title claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 34
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 31
- 238000005266 casting Methods 0.000 claims abstract description 17
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 17
- 239000004417 polycarbonate Substances 0.000 claims abstract description 17
- 239000011521 glass Substances 0.000 claims abstract description 15
- 229920000642 polymer Polymers 0.000 claims abstract description 10
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims description 14
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 10
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 8
- 230000037452 priming Effects 0.000 claims description 6
- 239000004014 plasticizer Substances 0.000 claims description 4
- 229920006397 acrylic thermoplastic Polymers 0.000 claims description 3
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 229920000193 polymethacrylate Polymers 0.000 abstract 1
- 239000012790 adhesive layer Substances 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 239000011229 interlayer Substances 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000002346 layers by function Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000006120 scratch resistant coating Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000003856 thermoforming Methods 0.000 description 2
- -1 triethoxysilyl Chemical group 0.000 description 2
- 208000032484 Accidental exposure to product Diseases 0.000 description 1
- 229920005440 Altuglas® Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920004142 LEXAN™ Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 231100000818 accidental exposure Toxicity 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000000475 sunscreen effect Effects 0.000 description 1
- 239000000516 sunscreening agent Substances 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000005341 toughened glass Substances 0.000 description 1
- QLNOVKKVHFRGMA-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical group [CH2]CC[Si](OC)(OC)OC QLNOVKKVHFRGMA-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/712—Weather resistant
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/72—Density
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/738—Thermoformability
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2551/00—Optical elements
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2571/00—Protective equipment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2605/00—Vehicles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2605/00—Vehicles
- B32B2605/006—Transparent parts other than made from inorganic glass, e.g. polycarbonate glazings
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2605/00—Vehicles
- B32B2605/18—Aircraft
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B64—AIRCRAFT; AVIATION; COSMONAUTICS
- B64C—AEROPLANES; HELICOPTERS
- B64C1/00—Fuselages; Constructional features common to fuselages, wings, stabilising surfaces or the like
- B64C1/14—Windows; Doors; Hatch covers or access panels; Surrounding frame structures; Canopies; Windscreens accessories therefor, e.g. pressure sensors, water deflectors, hinges, seals, handles, latches, windscreen wipers
- B64C1/1476—Canopies; Windscreens or similar transparent elements
- B64C1/1492—Structure and mounting of the transparent elements in the window or windscreen
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Aviation & Aerospace Engineering (AREA)
- Laminated Bodies (AREA)
Abstract
L'invention concerne - un vitrage comprenant au moins une feuille d'acrylique modifié, caractérisé en ce que celle-ci y est associée à au moins une autre feuille d'acrylique modifié, et/ou au moins une feuille de poly(méthacrylate de méthyle) (PMMA) issu de coulée, et/ou au moins une feuille d'un autre polymère transparent tel que polycarbonate (PC), et/ou au moins une feuille de verre notamment renforcé chimiquement, en un vitrage feuilleté et/ou multiple ; - son application pour un véhicule de transport aérien.The invention relates to a glazing unit comprising at least one modified acrylic sheet, characterized in that it is associated therewith with at least one other modified acrylic sheet, and / or at least one poly (methacrylate) sheet. methyl) (PMMA) from casting, and / or at least one sheet of another transparent polymer such as polycarbonate (PC), and / or at least one glass sheet, in particular chemically reinforced, in a laminated and / or multiple glazing unit ; - its application for an air transport vehicle.
Description
© N° de publication : 3 053 277 (à n’utiliser que pour les commandes de reproduction)© Publication no .: 3,053,277 (to be used only for reproduction orders)
©) N° d’enregistrement national : 16 56060 ® RÉPUBLIQUE FRANÇAISE©) National registration number: 16 56060 ® FRENCH REPUBLIC
INSTITUT NATIONAL DE LA PROPRIÉTÉ INDUSTRIELLENATIONAL INSTITUTE OF INDUSTRIAL PROPERTY
COURBEVOIECOURBEVOIE
©) Int Cl8 : B 32 B 27/30 (2017.01), B 32 B 27/08, 17/10©) Int Cl 8 : B 32 B 27/30 (2017.01), B 32 B 27/08, 17/10
DEMANDE DE BREVET D'INVENTION A1A1 PATENT APPLICATION
VITRAGE AERONAUTIQUE COMPRENANT UNE FEUILLE DE POLYMERE ACRYLIQUE A PROPRIETES MECANIQUES AMELIOREES.AERONAUTICAL GLAZING COMPRISING AN ACRYLIC POLYMER SHEET WITH IMPROVED MECHANICAL PROPERTIES.
FR 3 053 277 - A1 (üp) L'invention concerneFR 3 053 277 - A1 (üp) The invention relates
- un vitrage comprenant au moins une feuille d'acrylique modifié, caractérisé en ce que celle-ci y est associée à au moins une autre feuille d'acrylique modifié, et/ou au moins une feuille de poly(méthacrylate de méthyle) (PMMA) issu de coulée, et/ou au moins une feuille d'un autre polymère transparent tel que polycarbonate (PC), et/ou au moins une feuille de verre notamment renforcé chimiquement, en un vitrage feuilleté et/ou multiple;- a glazing comprising at least one sheet of modified acrylic, characterized in that the latter is associated therewith at least one other sheet of modified acrylic, and / or at least one sheet of poly (methyl methacrylate) (PMMA ) derived from casting, and / or at least one sheet of another transparent polymer such as polycarbonate (PC), and / or at least one sheet of glass, in particular chemically reinforced, in laminated and / or multiple glazing;
- son application pour un véhicule de transport aérien.- its application for an air transport vehicle.
VITRAGE AERONAUTIQUE COMPRENANT UNE FEUILLE DE POLYMERE ACRYLIQUE A PROPRIETES MECANIQUES AMELIOREESAERONAUTICAL GLAZING COMPRISING AN ACRYLIC POLYMER SHEET WITH IMPROVED MECHANICAL PROPERTIES
L’invention a trait aux vitrages aéronautiques dont l’utilisation est particulièrement exigeante : choc à l’oiseau, différences de pressions entre l’extérieur et l’intérieur, exposition à des températures très basses côté extérieur. Pour ces vitrages il est nécessaire de garantir un niveau élevé de résistance mécanique, de transparence et qualité optique préservées durablement.The invention relates to aeronautical glazing, the use of which is particularly demanding: bird strike, differences in pressure between the exterior and the interior, exposure to very low temperatures on the exterior. For these glazings it is necessary to guarantee a high level of mechanical strength, transparency and optical quality preserved over the long term.
ίο II est connu de modifier physiquement une feuille de matériau polymère tel qu’acrylique, notamment poly(méthacrylate de méthyle) (PMMA) par étirage, par exemple selon deux directions perpendiculaires dans le plan de la feuille (bi-étirage), pour lui procurer une résistance à la relaxation de contrainte par microfendillement, c’est-à-dire une haute qualité optique durable sous exposition au froid, à l’abrasion mécanique et aux composés chimiques, à l’humidité de l’air, ainsi qu’une aptitude à être percé nécessaire en cas de boulonnage du vitrage à la carosserie ou la carlingue d’un véhicule, un cadre ou une structure de montage, et une amélioration de la résistance mécanique (chocà l’oiseau...).ίο It is known to physically modify a sheet of polymeric material such as acrylic, in particular poly (methyl methacrylate) (PMMA) by stretching, for example in two perpendicular directions in the plane of the sheet (bi-stretching), for it provide resistance to stress relaxation by microcracking, that is to say a high lasting optical quality under exposure to cold, mechanical abrasion and to chemical compounds, to air humidity, as well as an ability to be drilled necessary in the event of bolting of the glazing to the bodywork or cabin of a vehicle, a frame or a mounting structure, and an improvement in mechanical resistance (bird strike, etc.).
Cependant le procédé d’étirage est délicat, long et coûteux (perte de matière, prix de la matière...). Le matériau ainsi étiré présente l’inconvénient de se désétirer lorsqu’il est soumis à des températures supérieures à 100 °C environ, limitant et compliquant les procédés de thermoformage : on thermoforme et on doit réétirer, on contraint par soufflage ou autre. Le matériau étiré présente donc un risque de perte de dimensionnement en cas d’exposition accidentelle.However, the drawing process is delicate, long and costly (loss of material, price of the material, etc.). The material thus stretched has the drawback of being stretched when it is subjected to temperatures above about 100 ° C., limiting and complicating the thermoforming processes: one thermoforms and one must stretch, one constrains by blowing or the like. The stretched material therefore presents a risk of loss of design in the event of accidental exposure.
L’invention s’est donné pour tâche d’utiliser des polymères transparents notamment acryliques comportant dans leur chaîne polymère des blocs nanostructurés et/ou additivés de micro- ou nanocharges limitant la propagation de fissure, pour des applications de vitrages de transport complexes à propriétés mécaniques renforcées sous la forme de vitrages feuilletés et/ou multiples, plans ou bombés. Ces polymères modifiés ne nécessitent pas de lourd procédé d’étirage et offrent une plus grande facilité de mise en forme par thermoformage (stabilité dimensionnelle); ils ne sont pas précontraints, présentent une sécurité accrue en cas d’exposition à la chaleur (hublots d’avion par exemple).The invention has given itself the task of using transparent polymers, in particular acrylic polymers, comprising in their polymer chain nanostructured blocks and / or additives of micro- or nanofillers limiting crack propagation, for applications of complex transport glazing with properties. reinforced mechanics in the form of laminated and / or multiple glazing, flat or curved. These modified polymers do not require a heavy drawing process and offer greater ease of shaping by thermoforming (dimensional stability); they are not pre-stressed, offer increased safety in the event of exposure to heat (aircraft windows, for example).
L’invention a donc pour objet un vitrage comprenant au moins une feuille d’acrylique modifié, caractérisé en ce que celle-ci y est associée à au moins une autre feuille d’acrylique modifié, et/ou au moins une feuille de poly(méthacrylate de méthyle) (PMMA) issu de coulée, et/ou au moins une feuille d’un autre polymère transparent tel que polycarbonate (PC), et/ou au moins une feuille de verre notamment renforcé chimiquement, en un vitrage îo feuilleté et/ou multiple.A subject of the invention is therefore a glazing unit comprising at least one sheet of modified acrylic, characterized in that the latter is associated therewith at least one other sheet of modified acrylic, and / or at least one sheet of poly ( methyl methacrylate) (PMMA) derived from casting, and / or at least one sheet of another transparent polymer such as polycarbonate (PC), and / or at least one sheet of glass, in particular chemically reinforced, in laminated glazing and / or multiple.
Au sens de l’invention on entend par « acrylique modifié » un polymère transparent acrylique modifié chimiquement pour améliorer ses propriétés mécaniques, qui présente les caractéristiques suivantes :Within the meaning of the invention, the term "modified acrylic" means a transparent acrylic polymer chemically modified to improve its mechanical properties, which has the following characteristics:
- Densité <1,2;- Density <1.2;
- Module en flexion > 2000, de préférence 2300 MPa ;- Flexural modulus> 2000, preferably 2300 MPa;
- Résistance au choc Charpy non entaillé > 35, de préférence 40 kJ/m2 ;- Charpy impact resistance not cut> 35, preferably 40 kJ / m 2 ;
- Transmission Lumineuse (longueurs d’onde du visible) > 90 % ;- Light Transmission (visible wavelengths)> 90%;
- Flou < 1 ;- Blur <1;
- Coefficient de Dilatation Thermique < 70 ppm / °K ;- Coefficient of Thermal Expansion <70 ppm / ° K;
- Résistance chimique : résistance au microfendillement au contact d’un cataplasme toluène / acétate d’isobutyle selon la norme militaire des Etats Unis d’Amérique MIL - P - 25690 > 17 MPa.- Chemical resistance: resistance to microcracking in contact with a toluene / isobutyl acetate poultice according to the military standard of the United States of America MIL - P - 25690> 17 MPa.
Un PMMA issu de coulée est connu offrir la meilleure qualité optique de transparence par rapport à un PMMA extrudé.PMMA from casting is known to offer the best optical quality of transparency compared to extruded PMMA.
Un vitrage feuilleté comporte plusieurs feuilles rigides transparentes minérales (verre) et/ou organiques (matériau polymère) reliées les unes aux autres par des couches adhésives intercalaires détaillées ci-dessous.A laminated glazing comprises several rigid transparent mineral (glass) and / or organic (polymeric material) sheets connected to each other by intermediate adhesive layers detailed below.
Un vitrage multiple est à plusieurs feuilles rigides transparentes monolithique et/ou feuilletées, minérales et/ou organiques, séparées les unes des autres par une lame d’air ou de gaz sec.Multiple glazing is made up of several rigid rigid monolithic and / or laminated, mineral and / or organic sheets, separated from each other by a layer of air or dry gas.
Toutes ces feuilles sont planes ou bombées.All these sheets are flat or curved.
De préférence, l’acrylique modifié est un polymère acrylique à propriétés mécaniques améliorées comportant dans sa chaîne polymère des blocs nanostructurés et/ou additivé de micro- ou nanocharges limitant la propagation de fissure.Preferably, the modified acrylic is an acrylic polymer with improved mechanical properties comprising in its polymer chain nanostructured blocks and / or additivated with micro- or nanofillers limiting crack propagation.
Dans une réalisation préférée mais non obligatoire de l’invention, le poly(méthacrylate de méthyle) (PMMA) issu de coulée est modifié physiquement pour résister à la relaxation de contrainte par microfendillement. La modification physique consiste notamment en un bi-étirage, elle est intéressante en ce qu’elle permet de percer le PMMA ou bien quand celui-ci est en face extérieure d’un vitrage soumis au froid, à l’abrasion mécanique, sans que des microfissures ne se forment dans la feuille de PMMA.In a preferred but not compulsory embodiment of the invention, the poly (methyl methacrylate) (PMMA) resulting from casting is physically modified to resist stress relaxation by microcracking. The physical modification consists in particular of a bi-stretching, it is advantageous in that it makes it possible to pierce the PMMA or else when the latter is facing the exterior of a glazing subjected to cold, to mechanical abrasion, without microcracks do not form in the PMMA sheet.
Selon d’autres caractéristiques préférées du vitrage de l’invention :According to other preferred characteristics of the glazing of the invention:
- une feuille d’acrylique modifié est collée à une autre feuille d’acrylique modifié ou à une feuille de poly(méthacrylate de méthyle) (PMMA) issu de coulée, ou bien encore à une feuille de verre par l’intermédiaire de polyvinylbutyral (PVB) exempt de plastifiant réagissant avec les acryliques, ou de polyuréthane thermoplastique (TPU) ;a sheet of modified acrylic is bonded to another sheet of modified acrylic or to a sheet of poly (methyl methacrylate) (PMMA) resulting from casting, or alternatively to a sheet of glass by means of polyvinyl butyral ( PVB) free of plasticizer reacting with acrylics, or of thermoplastic polyurethane (TPU);
- une feuille d’acrylique modifié est collée à une feuille de polycarbonate (PC) par l’intermédiaire de polyuréthane thermoplastique (TPU) ;- a modified acrylic sheet is bonded to a polycarbonate sheet (PC) by means of thermoplastic polyurethane (TPU);
- avant d’être collée à une autre feuille, la surface d’une feuille d’acrylique modifié, ou de poly(méthacrylate de méthyle) (PMMA) issu de coulée, est soumise à un traitement de primage ; le primage a pour effet d’améliorer la qualité et la durabilité du collage ; lorsqu’il est collé à une autre feuille, le verre notamment renforcé - trempé chimiquement peut aussi être primé, contrairement à une feuille de polycarbonate qui ne l’est jamais, car elle est particulièrement dégradée par de nombreux composés chimiques ;- before being bonded to another sheet, the surface of a sheet of modified acrylic, or poly (methyl methacrylate) (PMMA) resulting from casting, is subjected to a priming treatment; priming has the effect of improving the quality and durability of the bonding; when glued to another sheet, especially reinforced glass - chemically toughened can also be awarded, unlike a polycarbonate sheet which never is, because it is particularly degraded by many chemical compounds;
- au moins une feuille d’acrylique modifié est débordante par rapport aux feuilles du vitrage constituées d’un autre matériau, notamment quand la haute qualité mécanique de ce matériau est mise à profit pour percer les parties débordantes en vue d’un montage du vitrage par boulonnage ou équivalent, ou bien pour un montage du vitrage par pincement ;- at least one modified acrylic sheet projects beyond the glazing sheets made of another material, especially when the high mechanical quality of this material is used to pierce the protruding parts for mounting the glazing by bolting or equivalent, or for mounting the glazing by pinching;
- il est bombé.- it is curved.
L’invention a également pour objet l’application d’un vitrage tel que décrit précédemment comme vitrage pour un véhicule de transport aérien, notamment un hélicoptère ou un avion.The invention also relates to the application of glazing as described above as glazing for an air transport vehicle, in particular a helicopter or an airplane.
L’invention sera mieux comprise à la lumière des Figures 1 à 12 annexées, représentant toutes de manière schématique différentes réalisations de vitrages conformes à l’invention.The invention will be better understood in the light of Figures 1 to 12 appended, all schematically showing different embodiments of glazing according to the invention.
Tous les matériaux désignés ci-dessous par les mêmes termes sont identiques.All the materials designated below by the same terms are identical.
En référence à la Figure 1, un double vitrage conforme à l’invention est composéReferring to Figure 1, double glazing according to the invention is composed
- d’une feuille d’acrylique modifié 1 d’épaisseur au moins égale à 1, de préférence 1,5 mm, au plus égale à 25, de préférence 12 mm, commercialisée par la Société Arkema sous la marque enregistrée Altuglas® Shield Up,- a modified acrylic sheet 1 of thickness at least equal to 1, preferably 1.5 mm, at most equal to 25, preferably 12 mm, sold by the Arkema Company under the registered brand Altuglas® Shield Up ,
- d’une lame d’air 10, et- an air knife 10, and
- d’une feuille de PMMA issu de coulée 2, physiquement modifié tel que par étirage, ou non, d’épaisseur au moins égale à 0,5, de préférence 3 mm, au plus égale à 25, de préférence 8 mm, polymère acrylique de grade aéronautique commercialisé par la Société Evonik® sous la référence GS 249.- a sheet of PMMA from casting 2, physically modified such as by stretching, or not, of thickness at least equal to 0.5, preferably 3 mm, at most equal to 25, preferably 8 mm, polymer aeronautical grade acrylic marketed by Evonik® under the reference GS 249.
La feuille d’acrylique modifié 1 constitue de préférence la face extérieure du vitrage, c’est-à-dire exposée à l’atmosphère extérieure, mais il n’est pas exclu qu’elle en constitue au contraire la face intérieure, et que dans ce cas la feuille de polymère acrylique de grade aéronautique constitue la face extérieure du vitrage.The modified acrylic sheet 1 preferably constitutes the external face of the glazing, that is to say exposed to the external atmosphere, but it is not excluded that it constitutes on the contrary the internal face, and that in this case the aeronautical grade acrylic polymer sheet constitutes the outer face of the glazing.
Le vitrage représenté Figure 2 diffère de celui de la Figure 1 en ce qu’il est composé de deux feuilles d’acrylique modifié 1 et Tet en ce que la feuille 1, constituant la face extérieure du vitrage, a ici une épaisseur au moins égale à 0,5, de préférence 3 mm, au plus égale à 25, de préférence 8 mm, la feuille T étant identique à la feuille 1 de la Figure 1.The glazing shown in Figure 2 differs from that of Figure 1 in that it is composed of two sheets of modified acrylic 1 and Tet in that the sheet 1, constituting the outer face of the glazing, here has a thickness at least equal at 0.5, preferably 3 mm, at most equal to 25, preferably 8 mm, the sheet T being identical to the sheet 1 of Figure 1.
La Figure 3 représente un double vitrage composé d’un vitrage feuilleté à trois constituants 1, 3, 2, d’une lame d’air 10 et d’une feuille de PMMA issu de coulée 2’.Figure 3 shows a double glazing composed of a laminated glazing with three components 1, 3, 2, an air layer 10 and a sheet of PMMA from casting 2 ’.
La feuille d’acrylique modifié 1 est identique à celle 1 de la Figure 1. Les 5 deux feuilles de PMMA issu de coulée 2, 2’ ont une épaisseur au moins égale àThe modified acrylic sheet 1 is identical to that 1 in Figure 1. The 5 two sheets of PMMA from casting 2, 2 ’have a thickness at least equal to
0,8, de préférence 1,5 mm, au plus égale à 80, de préférence 12 mm.0.8, preferably 1.5 mm, at most equal to 80, preferably 12 mm.
La feuille d’acrylique modifié 1 et la feuille de PMMA issu de coulée 2 sont collées au moyen d’un adhésif intercalaire 3 d’épaisseur au moins égale à 0,1, de préférence 0,38 mm, au plus égale à 20, de préférence 2,5 mm, îo notamment égale à 1,25 mm.The modified acrylic sheet 1 and the PMMA sheet from casting 2 are bonded using an interlayer adhesive 3 of thickness at least equal to 0.1, preferably 0.38 mm, at most equal to 20, preferably 2.5 mm, in particular equal to 1.25 mm.
Selon une première variante, l’adhésif intercalaire 3 est constitué de polyuréthane thermoplastique (TPU) commercialisé par la Société Huntsman sous la marque enregistrée Crystalflex® PE 399 ou 499 et les feuilles d’acrylique modifié 1 et de PMMA issu de coulée 2 sont soumises, préalablement à l’assemblage en feuilleté, à un primage par une composition à base de méthacrylate de méthyle et d’organosilanes 1-Propanamine,3(triethoxysilyl) et de 2-Ethanediamine,N-[3-(trimethoxysilyl)propyl]-1 commercialisés sous les appellations respectives de DOW CORNING® Z-6011 SILANE et DOW CORNING Z-6020® SILANE.According to a first variant, the interlayer adhesive 3 consists of thermoplastic polyurethane (TPU) marketed by the Huntsman Company under the registered trademark Crystalflex® PE 399 or 499 and the sheets of modified acrylic 1 and of PMMA from casting 2 are subjected , prior to assembly in laminated form, to priming with a composition based on methyl methacrylate and organosilanes 1-Propanamine, 3 (triethoxysilyl) and 2-Ethanediamine, N- [3- (trimethoxysilyl) propyl] - 1 sold under the respective names of DOW CORNING® Z-6011 SILANE and DOW CORNING Z-6020® SILANE.
Selon une seconde variante, l’adhésif intercalaire 3 est constitué de polyvinylbutyral à plastifiant ne réagissant pas avec les acryliques, commercialisé par la Société Eastman Solutia sous l’appellation PVB DB 31 ou PVB DS 31 et les feuilles d’acrylique modifié 1 et de PMMA issu de coulée 2 sont soumises, préalablement à l’assemblage en feuilleté, à un primage par une composition à base de méthacrylate de méthyle.According to a second variant, the interlayer adhesive 3 consists of polyvinyl butyral with a plasticizer which does not react with acrylics, marketed by the company Eastman Solutia under the name PVB DB 31 or PVB DS 31 and the sheets of modified acrylic 1 and PMMA from casting 2 are subjected, prior to laminated assembly, to a priming with a composition based on methyl methacrylate.
La feuille d’acrylate modifié 1 constitue la face du vitrage extérieur au véhicule de transport (voire au bâtiment).The modified acrylate sheet 1 constitutes the face of the glazing exterior to the transport vehicle (or even to the building).
Est représenté sur la Figure 4 un vitrage feuilleté symétrique dans lequel deux feuilles de verre trempé chimiquement 4, 4’ d’épaisseurs au moins égales à 0,1, de préférence 0,55 mm, au plus égales à 20, de préférence 8 mm, sont collées de part et d’autre d’une feuille d’acrylique modifié 1 identique à celle de la Figure 1 par l’intermédiaire d’une couche adhésive intercalaire 3, 3’ identique à celle de la Figure 3 en polyuréthane thermoplastique.Is shown in Figure 4 a symmetrical laminated glazing in which two sheets of chemically toughened glass 4, 4 'of thickness at least equal to 0.1, preferably 0.55 mm, at most equal to 20, preferably 8 mm , are glued on either side of a modified acrylic sheet 1 identical to that of FIG. 1 by means of an intermediate adhesive layer 3, 3 ′ identical to that of FIG. 3 made of thermoplastic polyurethane.
Le vitrage de la Figure 5 ne diffère de celui de la Figure 4 qu’en ce que la feuille d’acrylique modifié 1 est débordante. La partie débordante de cette feuille peut être percée en vue d’un montage du vitrage par boulonnage, ou bien le vitrage monté avec pincement notamment de cette partie débordante.The glazing in Figure 5 differs from that in Figure 4 only in that the modified acrylic sheet 1 is overflowing. The projecting part of this sheet can be drilled for mounting the glazing by bolting, or the glazing mounted with pinching in particular of this projecting part.
Le vitrage de la Figure 6 est asymétrique et diffère de celui de la Figure 5 par la suppression d’une feuille de verre et de sa couche adhésive intercalaire associée d’un seul côté de la feuille d’acrylique modifié 1. Cette dernière est apte à constituer aussi bien la face extérieure qu’intérieure du vitrage.The glazing in Figure 6 is asymmetrical and differs from that in Figure 5 by the removal of a glass sheet and its associated adhesive layer on one side of the modified acrylic sheet 1. The latter is suitable to constitute both the outer and inner face of the glazing.
Le vitrage de la Figure 7 ne diffère de celui de la Figure 6, îo respectivement celui de la Figure 8 de celui de la Figure 5 que par l’ajout d’une couche mince fonctionnelle 20 sur la face interne au feuilleté de la feuille de verre 4, respectivement 4’. La couche fonctionnelle 20 est par exemple une couche chauffante telle qu’en oxyde d’indium dopé à l’étain (en anglais ITO pour Indium Tin Oxide), à fonction de dégivrage et/ou désembuage, ou une couche de contrôle thermique telle qu’antisolaire (réfléchissant le rayonnement solaire).The glazing of FIG. 7 differs from that of FIG. 6, respectively that of FIG. 8 from that of FIG. 5 only by the addition of a functional thin layer 20 on the internal face of the laminated sheet. glass 4, respectively 4 '. The functional layer 20 is for example a heating layer such as indium oxide doped with tin (in English ITO for Indium Tin Oxide), with defrosting and / or demisting function, or a thermal control layer such as 'sunscreen (reflecting solar radiation).
La Figure 9 ne diffère de la Figure 8 qu’en ce que les deux feuilles de verre 4, 4’ et non une seule portent sur leur face interne une couche fonctionnelle 20, 21.Figure 9 differs from Figure 8 only in that the two glass sheets 4, 4 ’and not just one carry on their inner face a functional layer 20, 21.
La Figure 10 représente un vitrage feuilleté de plusieurs feuilles d’acrylique modifié 1, T, 1” collées les unes aux autres par des couches adhésives intercalaires 3, 3’ de la manière décrite précédemment, après avoir été soumises à un traitement de primage. Dans tous les vitrages représentés ici, chaque feuille d’acrylique modifié 1, T, 1” peut être remplacée par un feuilleté similaire à celui de la Figure 10, tout comme chaque feuille de verre 4, 4’ peut être remplacée par un feuilleté de plusieurs feuilles de verre collées les unes aux autres par des couches adhésives intercalaires de PVB ou équivalent.FIG. 10 represents a laminated glazing of several sheets of modified acrylic 1, T, 1 "bonded to each other by intermediate adhesive layers 3, 3’ as described above, after having been subjected to a priming treatment. In all the glazings represented here, each sheet of modified acrylic 1, T, 1 ”can be replaced by a laminate similar to that of FIG. 10, just as each sheet of glass 4, 4 'can be replaced by a laminated sheet of several glass sheets glued to each other by interlayer adhesive layers of PVB or equivalent.
Sur la Figure 11, un vitrage feuilleté est constitué de deux feuilles d’acrylique modifié 1,1’ collées de part et d’autre d’une feuille de polycarbonateIn Figure 11, a laminated glazing consists of two sheets of modified acrylic 1,1 ’glued on either side of a polycarbonate sheet
5 d’épaisseur au moins égale à 1, de préférence 2,5 mm, au plus égale à 12 mm, au moyen de couches adhésives intercalaires 3, 3’ de polyuréthane thermoplastique (TPU).(ne comportant pas de plastifiant qui serait susceptible d’attaquer le polycarbonate), après que les deux feuilles d’acrylique modifié 1, 1’ ont été primées selon la première variante décrite ci-dessus.5 of thickness at least equal to 1, preferably 2.5 mm, at most equal to 12 mm, by means of intermediate adhesive layers 3, 3 ′ of thermoplastic polyurethane (TPU). (Not comprising a plasticizer which would be susceptible to attack the polycarbonate), after the two modified acrylic sheets 1, 1 ′ have been awarded according to the first variant described above.
L’invention s’étend aussi à un feuilleté comprenant la structure obtenue à partir de celle de la Figure 11, en en supprimant la feuille d’acrylique modifié 1 ’ et la couche de TPU 3’, et en revêtant la surface ainsi devenue libre de la feuille de polycarbonate 5 d’un revêtement ou vernis dur anti-rayure, notamment de type polysiloxane. On peut citer comme exemple de feuille de polycarbonate revêtue sur une face d’un revêtement anti-rayure une feuille commercialisée par la Société Sabic Innovative Plastics sous les marques enregistrées Lexan® îo Margard® HLGA3. La face de polycarbonate revêtue d’un revêtement dur antirayure constitue une face extérieure d’un vitrage feuilleté, destinée de préférence à être exposée à l’atmosphère d’un habitacle de véhicule de transport.The invention also extends to a laminate comprising the structure obtained from that of FIG. 11, by removing therefrom the modified acrylic sheet 1 ′ and the layer of TPU 3 ′, and coating the surface thus become free of the polycarbonate sheet 5 of a hard scratch-resistant coating or varnish, in particular of the polysiloxane type. An example of a polycarbonate sheet coated on one side with an anti-scratch coating is a sheet sold by Sabic Innovative Plastics under the registered trademarks Lexan® îo Margard® HLGA3. The polycarbonate face coated with a hard scratch-resistant coating constitutes an outer face of laminated glazing, preferably intended to be exposed to the atmosphere of a passenger compartment of a transport vehicle.
Le vitrage représenté sur la Figure 12 diffère de celui de la Figure 11 en ce que les feuilles d’acrylique modifié 1,1’ débordent de celle de polycarbonateThe glazing shown in Figure 12 differs from that in Figure 11 in that the 1.1 ’modified acrylic sheets protrude from that of polycarbonate
5. Ce dernier est fragile, ne peut pas être percé. L’espace vide à la périphérie de la feuille de polycarbonate 5 est bouché par des cales de compensation 30, 31 constitué par exemple de thermodurcissable, composite polyester méthacrylate de méthyle, époxy - fibres de verre, ... aptes à protéger le chant de la feuille de polycarbonate, tant mécaniquement que chimiquement.5. The latter is fragile and cannot be pierced. The empty space at the periphery of the polycarbonate sheet 5 is blocked by compensating shims 30, 31 consisting for example of thermosetting, polyester composite methyl methacrylate, epoxy - glass fibers, ... capable of protecting the edge of the polycarbonate sheet, both mechanically and chemically.
Pour fixer le vitrage dans son environnement de montage, on perce les parties débordantes des deux feuilles d’acrylique modifié 1, 1’ ainsi que les cales de compensation 30, 31 et l’on met en oeuvre des moyens de fixation adaptés tels que boulons, écrous... par vissage. Dans les trous percés dans les cales de compensation 30, 31 sont insérées des douilles de reprise d’effort non représentées pour éviter d’écraser les feuilles d’acrylique modifié 1,1’.To fix the glazing in its mounting environment, the protruding parts of the two sheets of modified acrylic 1, 1 ′ are drilled as well as the compensation shims 30, 31 and suitable fixing means are used such as bolts , nuts ... by screwing. In the holes drilled in the compensation shims 30, 31 are inserted force recovery sockets, not shown, to avoid crushing the 1.1 ’modified acrylic sheets.
Les vitrages selon l’invention sont parfaitement adaptés pour une application aéronautique, voire pour tous véhicules de transport (terrestres, aquatiques ou aériens) voire pour bâtiment présentant une exigence de sécurité, anti-effraction ou anti-pénétration. Ils constituent en particulier d’excellents vitrages d’avions ou hélicoptères de toutes tailles, pincés, boulonnés et/ou désembuants et/ou dégivrants.The glazings according to the invention are perfectly suited for an aeronautical application, or even for all transport vehicles (land, water or air) or even for buildings presenting a security, burglar-proof or anti-penetration requirement. They constitute in particular excellent glazing for planes or helicopters of all sizes, pinched, bolted and / or defogging and / or deicing.
Claims (9)
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1656060A FR3053277B1 (en) | 2016-06-29 | 2016-06-29 | AERONAUTICAL GLAZING INCLUDING AN ACRYLIC POLYMER SHEET WITH IMPROVED MECHANICAL PROPERTIES |
| EP17737003.8A EP3478500A1 (en) | 2016-06-29 | 2017-06-22 | Aeronautic glazing comprising a sheet of acrylic polymer having improved mechanical properties |
| US16/311,325 US11052986B2 (en) | 2016-06-29 | 2017-06-22 | Aeronautic glazing comprising a sheet of acrylic polymer having improved mechanical properties |
| CN201780038179.1A CN109311290B (en) | 2016-06-29 | 2017-06-22 | Aircraft glass comprising acrylic polymer sheets with improved mechanical properties |
| KR1020187036925A KR102359698B1 (en) | 2016-06-29 | 2017-06-22 | Aviation Glazing Comprising Acrylic Polymer Sheet With Improved Mechanical Properties |
| BR112018075787-0A BR112018075787B1 (en) | 2016-06-29 | 2017-06-22 | AERONAUTICAL GLAZING COMPRISING AN ACRYLIC POLYMER SHEET WITH IMPROVED MECHANICAL PROPERTIES AND ITS APPLICATION |
| CA3027874A CA3027874A1 (en) | 2016-06-29 | 2017-06-22 | Aeronautic glazing comprising a sheet of acrylic polymer having improved mechanical properties |
| RU2019100995A RU2737368C2 (en) | 2016-06-29 | 2017-06-22 | Containing an acrylic polymer sheet aircraft glazing, having improved mechanical properties |
| PCT/FR2017/051658 WO2018002481A1 (en) | 2016-06-29 | 2017-06-22 | Aeronautic glazing comprising a sheet of acrylic polymer having improved mechanical properties |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1656060 | 2016-06-29 | ||
| FR1656060A FR3053277B1 (en) | 2016-06-29 | 2016-06-29 | AERONAUTICAL GLAZING INCLUDING AN ACRYLIC POLYMER SHEET WITH IMPROVED MECHANICAL PROPERTIES |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| FR3053277A1 true FR3053277A1 (en) | 2018-01-05 |
| FR3053277B1 FR3053277B1 (en) | 2020-11-06 |
Family
ID=57045099
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| FR1656060A Expired - Fee Related FR3053277B1 (en) | 2016-06-29 | 2016-06-29 | AERONAUTICAL GLAZING INCLUDING AN ACRYLIC POLYMER SHEET WITH IMPROVED MECHANICAL PROPERTIES |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US11052986B2 (en) |
| EP (1) | EP3478500A1 (en) |
| KR (1) | KR102359698B1 (en) |
| CN (1) | CN109311290B (en) |
| BR (1) | BR112018075787B1 (en) |
| CA (1) | CA3027874A1 (en) |
| FR (1) | FR3053277B1 (en) |
| RU (1) | RU2737368C2 (en) |
| WO (1) | WO2018002481A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR3099131B1 (en) * | 2019-07-26 | 2021-09-03 | Saint Gobain | Lightweight, low drag aircraft window |
| FR3100155B1 (en) * | 2019-08-30 | 2021-09-03 | Saint Gobain | LOW POWER HEATING INSULATION GLASS AND HIGH MECHANICAL RESISTANCE |
| CN111923543A (en) * | 2020-07-17 | 2020-11-13 | 中国航空工业集团公司沈阳飞机设计研究所 | Transparent structure and aircraft canopy thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070235692A1 (en) * | 2006-03-28 | 2007-10-11 | Chifei Wu | Nanophase carbon black grafted with organic compound in situ, synthesis thereof and articles therefrom |
| CN101955572A (en) * | 2009-12-15 | 2011-01-26 | 黄石理工学院 | Method for preparing modified carbon nanotube and methyl methacrylate composite material by thermo-compression method |
| WO2012085487A1 (en) * | 2010-12-23 | 2012-06-28 | Arkema France | Crosslinked nanostructured cast sheets |
| WO2012136941A1 (en) * | 2011-04-07 | 2012-10-11 | Arkema France | Novel impact-reinforced acrylic material |
| FR3013508A1 (en) * | 2013-11-21 | 2015-05-22 | Commissariat Energie Atomique | PHOTOVOLTAIC MODULE, AND METHOD OF MOUNTING AND REPAIRING |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5648149A (en) * | 1994-03-29 | 1997-07-15 | Ppg Industries, Inc. | Adhesion of thermoset polyurethane to rigid transparent substrates |
| US20020110693A1 (en) * | 2000-12-14 | 2002-08-15 | Richard David A. | Glazing unit and method of making the same |
| FR2936524B1 (en) * | 2008-09-26 | 2010-09-24 | Arkema France | TRANSPARENT FLAT ARTICLE BASED ON NANOSTRUCTURE ACRYLIC MATERIALS |
| US20120094084A1 (en) * | 2010-10-15 | 2012-04-19 | William Keith Fisher | Chemically-strengthened glass laminates |
-
2016
- 2016-06-29 FR FR1656060A patent/FR3053277B1/en not_active Expired - Fee Related
-
2017
- 2017-06-22 KR KR1020187036925A patent/KR102359698B1/en active IP Right Grant
- 2017-06-22 US US16/311,325 patent/US11052986B2/en active Active
- 2017-06-22 RU RU2019100995A patent/RU2737368C2/en active
- 2017-06-22 CN CN201780038179.1A patent/CN109311290B/en active Active
- 2017-06-22 WO PCT/FR2017/051658 patent/WO2018002481A1/en unknown
- 2017-06-22 CA CA3027874A patent/CA3027874A1/en active Pending
- 2017-06-22 EP EP17737003.8A patent/EP3478500A1/en active Pending
- 2017-06-22 BR BR112018075787-0A patent/BR112018075787B1/en active IP Right Grant
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070235692A1 (en) * | 2006-03-28 | 2007-10-11 | Chifei Wu | Nanophase carbon black grafted with organic compound in situ, synthesis thereof and articles therefrom |
| CN101955572A (en) * | 2009-12-15 | 2011-01-26 | 黄石理工学院 | Method for preparing modified carbon nanotube and methyl methacrylate composite material by thermo-compression method |
| WO2012085487A1 (en) * | 2010-12-23 | 2012-06-28 | Arkema France | Crosslinked nanostructured cast sheets |
| WO2012136941A1 (en) * | 2011-04-07 | 2012-10-11 | Arkema France | Novel impact-reinforced acrylic material |
| FR3013508A1 (en) * | 2013-11-21 | 2015-05-22 | Commissariat Energie Atomique | PHOTOVOLTAIC MODULE, AND METHOD OF MOUNTING AND REPAIRING |
Also Published As
| Publication number | Publication date |
|---|---|
| US11052986B2 (en) | 2021-07-06 |
| KR102359698B1 (en) | 2022-02-10 |
| RU2019100995A (en) | 2020-07-29 |
| BR112018075787B1 (en) | 2022-08-16 |
| WO2018002481A1 (en) | 2018-01-04 |
| CA3027874A1 (en) | 2018-01-04 |
| FR3053277B1 (en) | 2020-11-06 |
| CN109311290A (en) | 2019-02-05 |
| RU2737368C2 (en) | 2020-11-27 |
| CN109311290B (en) | 2021-07-06 |
| KR20190025563A (en) | 2019-03-11 |
| US20190233078A1 (en) | 2019-08-01 |
| RU2019100995A3 (en) | 2020-07-29 |
| EP3478500A1 (en) | 2019-05-08 |
| BR112018075787A2 (en) | 2019-03-26 |
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